Metallizing non-metals



United States Patent O 3,518,066 METALLIZING NON-METALS `Robert L, Bronnes, Irvington, Ray C. Hughes, Ardsley,

and Richard C. Sweet, North Tarrytown, N.Y., assignors, by mesne assignments, to U.S. Philips Corporation, New York, N.Y., a corporation of Delaware Original application Dec. 26, 1962, Ser. No. 247,246, now Patent No. 3,339,267, dated Sept. 5, 1967. Divided and this application July 12, 1967, Ser. No. 671,509

Int. Cl. B32b 15/04 U.S. Cl. 29-195 1 Claim ABSTRACT OF THE DISCLOSURE A metal-to-ceramic seal in which the surface of ceramic body is covered with an active metal such as tantalum, columbium or vanadium which is covered with an oxidation resistant metal layer such as platinum or palladium, the latter being fusion bonded to the metal.

This application is a division of application Ser. No. 247,246, tiled Dee-26, 1962, now Pat. No. 3,339,267, dated Sept. 5, 1967.

Our invention relates to metallized nonmetals and in particular, to a metal surface on a nonmetal which can be sealed or bonded to another metaLThe invention specifically relates to a metal surface on a body of nonmetallic material, for example, a ceramic or vitreous material useful for hermetically sealing electrical devices or making an electrical connection to the surface of the body.

The production of mechanically strong, hermetic joints between metals and non-metallic materials, such as ceramics, has heretofore required relatively high temperatures which may, in some cases, such as quartz and glass, be injurious to the material. For instance, in the Well-known molybdenum-manganese process, after the molybdenum-manganese powder is applied to the surface of the body, it is necessary to sinter the powder at a temperature about l400 C., or just below the softening point of the ceramic, in order to obtain a mechanically strong joint.

The deposition of metals onto non-metallic surfaces by sputtering or evaporation is known in the prior art. However, as previously obtained, the metallized layers were so poorly adherent as to fail to form hermetic joints, and were either not wettable by solders and braze metals, or alternatively, if wettable, were completely soluble in molten solder or braze metal, being thus stripped away from the non-metallic surface by the action of molten solder or braze metal.

An object of our invention is to provide an improved hermetic seal between a non-metal and a metal.

Another object of our invention is to permit low temperature hermetic sealing of glass and ceramics to metals.

Another object of our invention is to provide bright, reflective tarnish-resistant metallic layers on non-meta1 lic surfaces.

Still another object of our invention is to provide electrically conductive, oxidation resistant layers on nonmetallic surfaces.

Another object of our invention is to produce mechanically strong electrical leads and terminations to non-metallic surfaces.

A still further object of our invention is to provide mechanical attachments of metallic members to nonmetals.

And another object of our invention is to provide for joining together two or more non-metals via metallic layers.

Patented June 30, 1970 ICC These and further objects of our invention will appear as the specification progresses.

In contrast, the principal feature of our invention lies in the provision of a composite metallic layer which is strongly adherent to non-metallic surfaces, while cornbining, at=the same time, the novel properties of being readily wettable by molten solders and braze metals, but presenting relatively insoluble underlying layers which are extremely resistant to complete dissolution and consequent stripping by molten solder and braze metals. This combination of properties of the metallization obtained according to our invention thus permits the attainment of strong, hermetic brazed or soldered joints between the thusly metallized non-metal and a metal surface. The unique.` composition of the composite metallized layer provides also for the production of adherent, metallically bright, tarnish and oxidation resistant coatings which are also resistant to prolonged action of all common acids, and are useful as reflective, electrically conductive, and resistive films.

Broadly stated, our invention contemplates forming a hermetic seal between a metal and a non-metal and involves applying by cathodic sputtering a first reactive metal which has a high energy of bond formation. Tantalum and lcolumbium provide extremely high values of this parameter and are therefore capable of chemically bonding with great energy and firmness to the non-metallic constituents in the substrate. Likewise, vanadium, and to a lesser extent, titanium, zirconium and hafnium satisfy this requirement. We, therefore,l prefer to employ, in our process, tantalum, columbium, vanadium, or combinations thereof, in order to obtain a strong bond with the substrate.

Because these metals tend to form stable oxides which are reducble only with extreme difficulty, it is not practicable to solder or braze directly to these metals. This diiculty, in accordance with our invention, is obviated by applying over the metal, also by cathodic sputtering, a metal of the platinum group. This latter metal does not form oxides which hinder subsequent solderability, and furthermore, it enters into solid solution with the underlying metal to form a very tenacious bond.

While We do not know precisely what does take place when the latter layer is cathodically sputtered onto the first layer, it is probable that some interdiffusion occurs with the formation of an alloy, or alloys of the metals. Discrete layers of platinum over tantalum for example, applied to a non-metallic surface would be expected to exhibit the individual properties of the two metals. Thus, the application of molten tin-lead solder to the surface should result in the complete dissolution of the platinum layer, exposing the tantalum layer, which, due to its tendency to acquire a tenacious oxide film, is not wettable by the solder. Thus, it would be expected that a metallization consisting of a discrete layer of platinum over tantalum would not be solderable and brazeable. Quite unexpectedly, we have found that the composite layer of platinum-tantalum produced by the method of our invention remains perfectly wettable during long periods of exposure to molten solder and braze metals, while at the same time resisting stripping by the molten phase.

As a metal of the platinum group, we prefer to use palladium or platinum which we have found not only readily permits soldering thereto but also is so strongly bonded to the underlying layer of tantalum, columbium, or vanadium that it cannot be readily stripped therefrom. The metallizing layer after being heated at 800 C. in hydrogen for one-half hour cannot be dissolved even in strong acids, aqua regia, or a combination of nitric, hydrochloric and hydroliuoric acids. While we have found this to be the case for platinum and palladium, we have reason to believe that the other metals of the platinum group, with the exception of osmium which readily oxidizes and is unsuitable, probably will also give good results. Gold and silver do not adhere well fore, for obtaining higher sputtering rates, employment of an atmosphere of high atomic weight is advantageous. Furthermore, in order that pure metals be deposited, the sputtering atmosphere rnust be incapable of reacting with the metal. Since these metals can react with more comwhen applied over the iirst metal and are thus unsuitable. mon gases, it is necessary to employ one of the rare gases.

The invention will be described in greater detail in Due to consideration of atomic weight, oost, and availconnection with the following illustrative examples and ability, argon is most suitable, and is preferred. Krypton accompanying drawing in which: and zenon, still heavier, may be used but due to scarcity FIG. 1 shows an apparatus for carrying out the method 10 and high cost are not generally used, while helium and according to the invention; neon are less advantageous due to their lower atomic FIG. 2 shows a sectional view of a metallized nonweights. l metallic body according to the invention; In carrying out the process according to our invention, FIG. 3 shows an electrical connection for a metalwe have employed an anode-cathode separation of about lized non-metallic body; and 4 cm., with electrodes in the form of discs, within the FIG. 4 shows a brazed joint between a metal member range of 21/2 to 3 1/2 inches (61A to 8% mm.), argon and a non-metallic body. pressure of 0.02 to 0.05 mm., and potential differences of A body 1 of non-metallic material such as glass or 3000 to 4000 volts.' ceramic, for example, steatites (MgO-SiOZ), ferrites After the cleaned surface 9 is coated to a thickness of (MFe2O4, where M is one or more metals), porcelains 20 about 1000 A. or more with the reactive bonding metal (feldspar, clay, silica), forsterite (ZMgO, SiOz), Zircon which is selected from the group consisting of tantalum, (2ZrOSiO2), titanium dioxide (TiOg), alumina (A1203), columbium, and vanadium, or alloys thereof, the cathode beryllium oxide (BeO), spinel (MgOAl2O3), magis replaced with a cathode which consists, at least in part, nesium oxide (MgO), silicon carbide (SiC), boron carof palladium or platinum, and a layer of this metal about bide (B4G), aluminum nitride (AlN), fused quartz glass, 25 1000 A. in thickness is deposited over the layer of aluminosilicate glasses, synthetic sapphire, is first subreactive bonding metal. jected to a cleaning operation since it is essential that Under the conditions specified hereinabove, experithe surface of the body be physically and chemically mentally determined rates of deposition of various metals clean. The cleaning methods employed are governed by onto the surface to be coated were as follows:

Cathode Argon Deposition Cathode diameter pressure Voltage Current Time rate (mg./ Thickness of metal (in.) (y) (kv.) (ma.) (min.) @na/min.) deposit (A.)

3% 30 3. 5 50 10 o. 04 2, 40o 3% so 3 so s .o7 2,400 3% 50 3. s 10o 10 03 3, 600 3% 50 3. s 100 15 01 2, 500 2% 30 3. 5 30 12 1 6,000 2% 50 4. 0 60 4 3 6, 000 3 30 3. 5 30 11 06 6, 000 3 50 4.0 00 5 09 0,000

the chemical properties of the non-metal. For acid and After surface of body 1 has been metallized, the water resistant materials such as fused quartz, glass and body is removed from chamber 2 and can be joined, if aluminum oxide, the body is rst washed in hot Water, desired, to a further metal member by soldering or then soaked in a chromic acid cleaning solution, rinsed brazing. The metallized surface of the body, as shown in in hot tap water, rinsed in distilled water, rinsed in FIG. 2, has a thin layer 10 of tantalum, columbium, alcohol or acetone, and dried in an oven at 100 to 125 or vanadium which is firmly bonded to the substrate 11, C. Alternatively, refractory materials may be air-fired probably by a metal-to-non-metal bond. When a layer at suitable temperatures, after rinsing in distilled water, 12 of the metal of the platinum group is then sputtered within the range of 600 to 1000" C., to remove any onto this layer; some interdilfusion with the formation surface contaminants. of an alloy, or alloys 13 occurs at the inerface of the latter The cleaned body 1 is placed in a suitable chamber 2 layer and the layer 10. While the mechanism of this which can be evacuated and filled with an inert gas reaction is not fully understood, it is believed that due through a valve 3 at a pressure of the order 0.0l-0.1. mm. to sputtering, ions of the metal of the platinum group are mercury. Anode and cathode electrodes 5 and 4, respecof such energy that they penetrate into the rst layer so tively, have a potential applied therebetween at which an that a solid solution in the region of the interface is electrical discharge generally known as a glow discharge formed. Consequently, there is no sharp transition but is established between the two electrodes, and a current rather, a gradual transition between the reactive bonding flows. Under the action of this discharge, and due to metal and the metal of the platinum group. bombardment of the cathode surface by energetic ions That discrete layers are not formed is supported by the derived from the residual gas, the cathode 4, which condiscovery that the metal of the platinum group cannot be sists of tantalum, columbium, or vanadium is gradually readily stripped from the surface of the body. It is comdisintegrated and the metal deposited throughout the pletely resistant to strong acids, such as hydrofluoric chamber. In order to avoid overheating the anode and (HF), nitric (HNO3) and hydrochloric (HC1) acids. It cathode, water-cooling is supplied through ducts 6 and cannot be removed with aqua regia or with a combination 7. The anode is connected to ground through base plate of HF, HC1, and HNO3. Yet, this metallized surface can 8 of the vacuum apparatus and the cathode connected to be soldered to another metal member using such solders the negative terminal of a power supply. as tin-lead, copper, and gold indicating that the surface Practical conditions for cathodic sputtering of metals exhibits predominantly the alloy-forming characteristics at substantial rates involve pressures of the order of of a metal of the platinum group. Structures as shown 0.01-0.1 mm. of Hg, a potential difference between the in FIG. 2 are also useful as reflective surfaces by reason electrodes of 500-4000l volts, cathode current densities of of the bright metallic surface layer of platinum. Such 0.1 to 1.0 ma./cm.2, and an anode-cathode separation layers are also electrically conductive. of 5 to 20 cm. such that the anode and surface to be The resultant metallized body can be soldered or coated are outside the cathode dark space. These values brazed to another metal member so that a hermetic seal are representative, and are not absolute limits, however. can be formed. Alternatively, a conductor can be soldered 'Ihe sputtering rate of a given metal increases with into the metallized surface to provide a conductive contact creasing atomic Weight of the gas atmosphere; thereon the surface of the non-metal.

Thus, as shown in FIG. 3, a copper conductor 15 is attached by means of tin-lead solder joint 14 to the platinum layer 12. This allows electrical connections to be made to the electrically conductive surface layer of the non-metallic body, and permits the latter to be used as a circuit element or a terminal connection.

FIG. 4 illustrates a composite body formed by high temperature copper brazing a metal member 16 to the metallized surface of a non-metallic substrate 11. Due to actionat high temperature of molten copper, extensive diffusion and intermingling of the various metallic layers occurs resulting in the formation upon soldification of a metallic layer 17 in which the copper braze metal is extensively intermingled with the tantalum-platinum layer.

Thus, while we have described our invention in connection with specific examples and applications thereof, other modifications will be apparent to those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claim.

We claim:

1. A ceramic-to-metal seal comprising a ceramic body References Cited UNITED STATES PATENTS 3,106,489 10/1963 Lepselter 117-217 3,218,194 11/1965 Massel 117-217 3,265,473 8/1966 Gallet 29--195 L. DEWAYNE RUTLEDGE, Primary Examiner E. L. WEISE, Assistant Examiner U.S. C1. X.R. 29-198 

